Process for the manufacture of acrylonitrile polymer solution



umm(%) Sept 28, 1965 t MAsAKAzu TANIYAMA ETAL. 3,208,952

PROCESS FOR THE MNUFACTURE OF ACRYLONITHILE POLYMER SOLUTION Filed nec. 28. leso Ha P11418?, PH 1.a@

0 i0 /za fio 20 aan au FW@ ZM (Mr) nited States The present invention relates to a process for the manufacture of acrylonitrile polymer solu-tion `by polymerizing acrylonitrile with or without copolymerizable mon-omers in an yaqueous solvent containing zinc chloride as principal constituent, where hydrogen peroxide is effectively used with some `accelerators.

Hitherto, it has :been Well-known that in order -to prepare polymer solution including only polyacrylonitrile or polymers including acrylonitrile as a principal constituent in a solvent capable of dissolving both of these polymers and monomers, -for example, an aqueous zinc c-hloride solution. Toaccomplish this process, so-ca'lled solution polymerization, various types of polymerization initiators have been used by trial.

However, in order to make the process more valuable industrially, it is positively requested that the process enables to prepare m-ouldings with a high degree whiteness, such as iibers, -from a colorless, clear, transparent solution of polymer `without any defects, s uch as contamination of solvent due to the decomposition of polymerization catalysts, accumulation of insoluble substances and coloring of polymer solution and that the process has, in addition, merits to recover and purify Ithe solvent easily. Most well-kn-own processeswhere so-called Redox initiatorie. a combination of the persulfate with a suitable reducing agent, such as an organic amine, :formaldehyde sodium sulfoxlatc, or sodium bisulte are available, are too unsatisfactory to fulll the above mentioned Irequirements. In such cases, the polymer solution becomes colored and recovery of solvent is extremely complicated due to impurities formed. On the contrary, such unsatisfactoriness can be removed by using hydrogen peroxide, chloric acid or perchloric acid independently, lbecause H2O2 decomposes into O2 and H2O, while HClO3 and HC104 decompose respectively into O2 and HCl. However, this process also has disadvantages, such 'that the polymerization reaction is extremely slow or the introduction period is too long, or the relative conversion is too low, which are vvery unfavorable from the standpoint of industrial scale of production.

The present inventors have attained'la surprisingly important information as follows, as `a result of the various investigations.

Namely, in the polymerization of acrylonitrile or monomer mixture mainly containing acrylonitrile in an aqueous solvent containing zinc chloride yas a principal constituent by using hydrogen peroxide, it has [been ascertained that when hydrochloric acid or phosphoric acid ordinarily -considered as a decomposition inhibitor for hydrogen peroxide is added, the polymerization is unexpectedly laccelerated. 'In this case, it is astonishing that other acids indicate no significant effect. (Ref. Ta'ble No, 1.) On the other hand, it has also been found that the combination of various types of oxygen acids of chlorine with hydrogen peroxide not only alleviates the above mentioned disadvantage but the polymerization reaction is remarkably accelerated. Moreover, in the case of hydrochloric acid or phosphoric acid, adequate additional amounts are in the :range of 0.25 to 4% in net weight -for solvent solution. Either below 0.25% or ice above 4%, the effect is reduced, while it is desirable that the effective amount of -oxygen acids of chlorine should be from 0.1 to 10.0 moles per mole of hydrogen peroxide, and moreover, that the total iweight of hydrogen peroxide and oxygen acids of chlorine should be from 0.1 to 10.0% by weight of monomers to be polymerized. Furthermore, in this case contrary to the case, of oxygen acids of chlorine alone, no coloration occurs in the polymer solution.

The effects of several acids on polymerization are shown in Table 1 and FIG. l and FIG. 2, where the polymerization is performed at 60 C. with a monomer solution pre-pared iby mixing 10 parts of acrylonitrile with 90 parts of 60% aqueous zinc chloride solution, to which 1.5 parts of H2O2 is added. In table, average molecular weights are those calculated iby Staudingers formula:

17sp/c=2.83 X105 X 17sp=Specifc viscosity (=Average molecular weight) TABLE 1 Net additional acid/ solvent (weight percent) Time of polymerization (min.)

Relative conversion degree Molecular Kind of acid added weight None HC1 ACOII Formic acid Phosphoric acid Sulfurlc acld Table 2, shown as follows, represents the relation between x-value in oxygen acids HClOX (x24, 3, 2'or 1) used with hydrogen peroxide as initiator, and the time (hours) which has been taken to attain the ball-fall viscosity, 20 seconds at 60 C., of the polymer solution, which is prepared by adding to 90 parts aqueous solution comprising 40% zinc chloride and 20% sodium chloride, l0 parts monomer of a composition containing acrylonitrile and methyl acrylate in 9:1, and 0.1 part of the initiator composed of hydrogen peroxide and the above mentioned oxygen acids, HClOx, and by heating at 60 C. Here, for example the polymer solution showing the ballfall viscosity 20 at 60l C. is obtained by dissolving polyacrylonitrile of Staudingers molecular weight: 53,000 in 10% concentration in the above mentioned solvent. The present inventors have ascertained that this polymer solution is one of the most suitable solutions for moldings such as bers.

TABLE 2 O (Le. H201 only) only) 8 Above 10.

No polymerizatlon.

1 Almost no polymerization.

3 Moreover, in this case it is found that not only oxygen acids of chlorine but their metallic salts also shows similar effects. It'should be desirablenthat the metallic ions of those salts are preferably the same as those of the vinorganic salts of which the solvent is consisted, for the reason that the decomposition products from these salts should give no unfavorable effects on' the recovery of the..solvent.y i

The present invention provides a new process of solution-polymerization, based on the above described teach ings. However, in order to carry out this solution-polymerization process advantageously on industrial scale, it is effective to adopt the following polymerization process. v

`This will now be described in further detail.

The

polymerization initiators above described frequently generate av large quantity of the decomposition gas (consisting mainly of oxygen), which lis included in the polymer solution, and can not readily be eliminated even` in a long continuous defoaming operation, and moreover, a careless polymerization frequently grows insoluble gellike substance.

teachings, these troubles would -disturb the adaptation of the transparent colorless polymer solution prepared in constant quantity forvmoulding "operatiomsuch las spinning, with high eiliciency. Namely, according to the f present inventors investigation, since hydrogen peroxide readily decomposes to generate gases in an aqueoussolutioncontaining zinc chlorideas a principal constituent, the mixing of hydrogen peroxide in a solvent solution prior to polymerization causes the resulting polymer solution not only to occlude many foams,l but also thev 'given' concentration of the initiators clan not be maintained and the state ofpolymerization results in B-In case of polymerization in n pressured vessel. C-In case ol thev process according to the present invention.

Thus, according to this process, no water vapor .is generated, and accordingly formation of insoluble gel-like sub stances can be avoided. Namely, as described above the present inventors have proceeded the investigations from the standpoint of industry. As the result, foamless spinning solution can be manufactured, and the polymerization process can be continuously combined withthe spinning process, thereby the conventional system, which is In the production of the polymer solution on industrial scale based on the abovementioned newL divided into several processes--polymer production, polymer dissolution, filtration, defoamation and spinning, respectively-can be extremely simplified. Thus, the present inventors have succeeded in -acquiring unexpected economical advantages in industry, particularly such as losing reproducibility. The .same thingv can-be said also in the case of oxygen-acids of chlorine. On the other hand, when those initiators are added to a solvent solution containing monomers and left as it is, an undesirable polymerization will proceed even atv room temperature -to cause insoluble high molecular substances yto occur.

Inl order toavoid these difficulties, it has been observed that when the mixture is prepared with the solvent, monomers-and initiatorythen without delay isvpolymerized vatea lgiven temperature, the better results have been obtained `b ut -still not perfect. This point has further been studied and found that the foamation is'vnot merely due` to decomposition of initiator and the formation of insoluble gel-like substance is notv merely due to undesirable polymerization. In particular, the occurrence of foams is caused bythe gasification of residual monomers, especiallyr acrylonitrile, during the coursev of thermal polymerization, and by involving gases in Vthe vacant space ofthe polymerization vessel by stirring viscous liquid during polymerization `for making uniform solution. One theotherhand, the formation Vof insoluble gel-like substancesis dueto the fact that in the reaction system the water and residual monomer, those which evaporate in the vacant space and condense on the inner wall of the vessel, drop into the polymerl solution and cause its `local coagulation.

It is found that gasification of the .monomers is possible to bel suppressed by giving some pressure to the reaction system and that thel involving of gases is possible to be removed by filling -up the vessel with the polymer solu-v any vacant space inthe vessel according to the abovementioned informations, as compared with other solu. tron-polymerization process.

saving of construction expenses, preventing loss of intermediates, maintaining uniformity in quality of products, shortening of the operation time and saving of labor.

In short, thel presentA invention offers an entirely new and industrially surprising process, based. on the above described teachings, to provide a foamless, colorless, transparent polymer solution which is preparedby solution polymerization of acrylonitrile or monomer mixture' containing acry'lonitrile as a principal constituent in aqueous salt solution mainly containing zinc chloride, with hydrogen peroxide as aninitiator and which is spinnable iinmediately after the polymerizationl process.

In the realization of the present invention, not only an aqueous solution'containing zinc chloride alone but also aqueous solutions which contain zinc chloride as a principal constituent, mixed with some inorganic salts (such as sodium chloride, ammonium chloride, magnesiumA chlo ride, or Acalcium chloride), or' mixed with some organic compounds (such vas alcohols, ketones or nitriles) in such mutual proportions that both the monomers and the polymer can be dissolved, may be used.

rIhe'monomers available withacrylonitrile are allyl n salts, allyl sulfonic acid and its metallic salts, but, of

course, available monomers should be 'not necessarily those materials only.

' Example 1 flow hole by filling up the vessel with the monomerv soluv tion, in such a way that the concentration of H2O, was constantly 0.18% for the weight of the said monomer solution. When the said solutionfor polymexizatonwas controlled to flow through-the'vessel in two hours under gauge pressure of 1.7 k'g./'cm., the solution reached directly to spinnerets 'and was -spun out in a coagulating bath comprising 12% aqueous zinc `chloride solution as an ordinary wet spinning processfand a good ber was obtained substantialiywithout. trouble. V'Ihus 'produced' polymer had a molecular weight of 75,000 and the rela- Example 2 To 90 parts of 60% aqueous zinc chloride solution were added 0.8 part of phosphoric acid, 9 parts of acrylonitrile and 0.3 part of acrylic acid, and nally added 1.8 parts of 10% hydrogen peroxide solution. Then, a pressure vessel equipped with a stirrer was immediately tlled up with the resulting solution, and heated at 60 C. for 200 minutes under the pressure of kg./cm.2 (gauge pressure). Then, a quite clear foamless polymer solution was obtained at a relative conversion of 96% including polymer of molecular weight of 94,500. Then, the said solution is transferred to a spining device' and spun out through spinning nozzle in 15% aqueous zinc chloride solution to form a good fiber. The liber showed a dry strength of 3.6 g./d.; elongation of 30.2%; knot strength of 2.5 g./d. and knot elongation of 20.1%

Example 3 To 90 parts aqueousv solution comprising 56% zinc chloride and 4% sodium chloride were added l0 parts of acrylonitrile and 0.16 part of sodium perchlorate monohydrateto obtain a homogeneous solution. Thereupon, 0.60 part of H2O2 aqueous solution was added in the solution and it was immediately heated at 60 C. for 90 minutes, then a perfectly colorless transparent polymer solution was obtained. This solution was transfused to a spinning device wherein it was spun out in a coagulation bath comprising 14% zinc chloride and 1% sodium chloride. Then, it could be spun easily where the molecular weight of the polymer in the spinning solution was 94,000 and the relative conversion reached 95.6%, and the ballfall viscosity of the polymer solution was 108 seconds at 60 C.

Example 4 A pressure vessel as a polymerization apparatus was lilled up with a mixture of 89 parts'of60% aqueous zinc chloride solution, 9.9 parts of acrylonitrile and 0.7 part of methyl acrylate. Then, successively thev solution having above composition was fed continuously into the vessel maintaining the pressure 3 lig/cm.2 and heated at 40 C. and simultaneously 15% aqueous zinc chlorate solution and 9% aqueous H2O2 solution was pressed into the vessel through other inlets, separately, in such a way that the ratios of said two substances to 100 parts of said monomer solution can `be kept 0.75 part and 0.09 part in net'weight, respectively. By passing said solution through the polymerization device in 6 hours, a foamless colorless clear solution containing no insoluble substances could be obtained continuously. Thus produced polymer solution showed 83 seconds in ball-fall viscosity, and a relative conversion of 94.5% and the molecular weight lof polymer in the solution is 88,900. It could be spun easily by an ordinary method to form a good fiber having the dry strength :3.15 g./d., elongation 31.3%, knot strength 2.7 g./d. and elongation 22.0%.

Example 5 To parts of aqueous solution comprising 58% zinc chloride and 4% potassium chloride was added a monomer solution comprising 14 parts of acrylonitrile and 1 part of N-vinyl4--hydroxy-ethyl-imidazol. The resulting monomer s-olution, 0.32. part of 10% ,aqueous solution of potassium chlorite and 0.15 part of 10% aqueous solution of hydrogen peroxide were, separately, charged into a vessel as described in Example 1. Maintaining said proportions, the three solutions were continuously fed under the pressure of 0.4 kg./cm. being kept any foams out of the polymerization system. The reaction mass passed through the vessel being heated at 70 C. in two hours, then was obtained a transparent and homogeneous polymer solution in which the relative conversion reaches 89% and molecular weight of the polymer reaches 66,000. It had the viscosity of 42 seconds at 60 C., and immediately could be spun to form a good liber having an excellent dyeing property for acid dyestuls.

Example 6 As in Example 2, partsl of aqueous solution comprising 48% zinc chloride and 10% calcium chloride was -admixed with 9.5 parts acrylonitrile, 0.5 part lbutyl acrylate, 0.02 part calcium hypoclhlorite as well as finally with 0.04 part of 30% hydrogen peroxide aqueous solution, then the resulting solution was charged into a pressure vessel which was heated at 50 C. under the pressure of 2.2 kg./cm.2 for 4 hours. Thus, a transparent foamless polymer solution was obtained, having a ball-fall viscosity of seconds atv 60 C., relative conversion of 85% and a molecular weight of 103,000.

What we claim:

In a process for the aqueous solution polymerization of a polymerizable monomer comprising acrylonitrile in in the presence of zinc chloride and hydrogen peroxide, the improvement which comprises conducting said polymerization in the presence of from 0.1-10.0 moles of the salt of an oxygen acid of chlorine per mole of hydrogen peroxide, wherein the total weight of hydrogen peroxide and the salt of the oxygen lacid of chloride employed is in the range of from 0.1 to 10.0 weight percent based 0n said polymerizable monomer, and charging the resulting solution into a pressure vessel.

References Cited by the Examiner UNITED STATES PATENTS 1/57 Mallison 26o-85.5 6/58 Stanton et al. 260--29.6 

